CN110713771A - Waterproof emulsion and preparation method thereof - Google Patents
Waterproof emulsion and preparation method thereof Download PDFInfo
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- CN110713771A CN110713771A CN201910986020.3A CN201910986020A CN110713771A CN 110713771 A CN110713771 A CN 110713771A CN 201910986020 A CN201910986020 A CN 201910986020A CN 110713771 A CN110713771 A CN 110713771A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses waterproof emulsion and a preparation method thereof, belonging to the field of coatings. The emulsion prepared by the invention has no amine raw material, so that the emulsification effect of the emulsion is enhanced, the possibility of generating ammonia gas by hydrolysis can be reduced by introducing sulfonic acid groups when the emulsion is alkaline, and meanwhile, the hard segment in the emulsion can form hydrogen bond connection with the amine-free raw material of the emulsion, so that the mechanical property and the tensile property of a glue film formed by the emulsion are improved; the prepared waterproof auxiliary agent provides association points so that hydrophobic groups are not easy to extract and are well stored in a network structure of the emulsion adhesive film, and the hydrophobic property of the adhesive film is improved; the mixed monomer is introduced to perfect the performance of the emulsion, so that the emulsion has better adhesive force, aging resistance and mechanical property, and the obtained waterproof emulsion has excellent performance and can be firmly attached to a substrate for coating protection. The invention solves the problems that the prior waterproof emulsion can release ammonia gas harmful to human body in alkaline environment and the mechanical property and waterproof property of the coating are poor.
Description
Technical Field
The invention relates to the field of coatings, and particularly relates to a waterproof emulsion and a preparation method thereof.
Background
The coating is a building material with a long history, and along with the development of the society, the types of the coating are more and more; indoor paints have been described as being largely classified into two types, water-based paints and solvent-based paints. The pollution is mainly generated by solvent paint, and the worry of the pollution of the paint can be completely avoided by using environment-friendly water paint. Experts in the china coatings industry association believe that any solvent-borne coating will contain 50% or more organic solvent. Most of solvent-borne coatings and organic solvents contain benzene and compounds thereof, so that the solvent-borne coatings and the organic solvents cause serious harm to human bodies after long-term contact. Therefore, more and more people prefer to select environmentally friendly and non-toxic water-based coatings. The key to the good and bad waterproof effect of the building lies in whether the waterproof material is advanced, scientific and durable. The waterproof coating is a building coating which is widely applied at present, and the traditional waterproof materials such as asphalt and asphalt felt have the defects of easy aging, short service life, high construction difficulty, high cost and the like; modified asphalt coiled material, APP, SBS coiled material, BBI mortar waterproof material etc. are not ageing-resistant, and the water proofness is not good, receives temperature variation influence back, and the coiled material is very easily separated from the base member, produces shortcomings such as breach and hollowing, and the joint is easy to split. The waterproof principle of these conventional waterproofing agents is to block the pores of the masonry material to exclude the intrusion of external moisture, and since the pores are blocked to make the wall airtight, when moisture is drained from the masonry pores, it breaks the waterproof coating on the surface, resulting in a short coating life. In addition, the materials are not easy to construct at the complicated parts of the building, have high technical requirements, and are time-consuming and labor-consuming. The waterproof coating mainly comprises a single component and a double component, particularly the double component waterproof coating which is favored by consumers due to excellent mechanical property and compactness. However, with the expansion development of economy, environmental pollution and national outbreak of severe haze in the atmosphere have seriously threatened the environment on which Chinese people live, and VOC in coatings and adhesives are the first culprit to cause severe haze in the atmosphere and are the most important cause of haze. Although the performances of the existing water-based paint cannot exceed those of the traditional solvent-based paint, the water-based paint is a necessary development trend of waterproof paint due to no pollution, environmental protection and safety and environmental protection policy compliance, the original solvent-based paint enterprises are gradually eliminated, more strict regulations are correspondingly issued in various cities, and the solvent-based paint and solvent-based adhesive are forbidden to be used. The existing two-component waterproof coating has two important defects, one of which is that in the traditional two-component waterproof coating system, in order to ensure that a coating has certain mechanical property, the coating emulsion contains amine functional monomers. After the emulsion is mixed with powder materials such as cement, most of the mixture is strong alkaline. In an alkaline environment, the amine groups can be rapidly hydrolyzed, a large amount of ammonia gas harmful to human bodies is released, and the surrounding air environment is seriously damaged. Secondly, after the amine group is hydrolyzed under the alkaline condition, the mechanical properties of the coating, such as elongation at break, tensile strength and the like, are greatly reduced, and the specific expression is that the coating has stronger brittleness, and has the phenomena of cracking, water seepage and the like. Therefore, how to develop a waterproof emulsion which can not release harmful gas and has good mechanical property is a technical problem in the waterproof emulsion industry at present.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the problems that the prior waterproof emulsion can release ammonia gas harmful to human body in alkaline environment and the mechanical property and waterproof property of the coating are poor, the waterproof emulsion and the preparation method thereof are provided.
In order to solve the technical problems, the invention adopts the following technical scheme:
a water-proof emulsion comprises an amine-free raw material of the emulsion, a water-proof auxiliary agent and a mixed monomer.
The preparation method of the amine-free raw material of the emulsion comprises the steps of taking an amine-free functional monomer, adding an alcohol reaction additive according to the mass ratio of 2 ~ 5: 3 ~ 7, mixing, introducing nitrogen for protection, adding pentaerythritol diphosphite and diisodecyl diphosphite with the mass of 0.2 ~ 0.5.5% of the amine-free functional body, stirring and mixing to obtain a stirring mixture, adding adipic acid into the stirring mixture according to the mass ratio of 40 ~ 50: 5 ~ 9, adding dibutyltin diacetate with the mass of 1 ~ 5% of the stirring mixture, heating to 140 ~ 170 ℃, keeping the temperature, heating to 200 ~ 220 ℃, keeping the temperature, heating to ~ ℃, keeping the temperature, and distilling under reduced pressure to obtain the amine-free raw material of the emulsion.
The amine-free functional monomer is as follows: taking any one of 1, 3-dicarboxylic acid-5-sodium sulfonate, isophthalic acid dimethyl ester-5-sodium sulfonate, isophthalic acid-5-sodium sulfonate and isophthalic acid dihydroxy ethyl ester-5-sodium sulfonate to obtain the compound.
The alcohol reaction additive is: and taking any one of 1, 4-cyclohexanedimethanol, 2, 4-trimethyl-1, 3-pentanediol, 2-dimethyl-3-neopentyl glycol hydroxypropionate and neopentyl glycol to obtain the compound.
The preparation method of the waterproof auxiliary agent comprises the steps of taking isomeric fatty tridecanol polyoxyethylene ether, adding triethylamine to the isomeric fatty tridecanol polyoxyethylene ether according to the mass ratio of 1 ~ 3: 2 ~ 4, mixing to obtain a mixture, adding dichloromethane to the mixture according to the mass ratio of 2 ~ 5: 10 ~ 20, stirring and mixing to obtain a stirred mixture a, taking an acyl chloride additive according to the mass ratio of 1 ~ 3: 5 ~ 10, adding dichloromethane to the stirred mixture a, mixing to obtain a mixed solution, dropwise adding the mixed solution into the stirred mixture a according to the mass ratio of 1 ~ 3: 5 ~ 10, controlling the dropwise adding time to be 60 ~ 90min, stirring and mixing, carrying out suction filtration, taking suction filtration residues, carrying out rotary evaporation, taking rotary evaporation residues, and carrying out vacuum drying to obtain the.
The acyl chloride additive is prepared by adding acryloyl chloride into lauroyl chloride according to the mass ratio of 4 ~ 7: 1 ~ 3 and mixing.
The mixed monomer is prepared by mixing, by mass, 3 ~ 7 parts of dodecafluoroheptyl methacrylate, 3 ~ 6 parts of vinyl acetate, 2 ~ 6 parts of perfluorohexyl ethyl acrylate, 2 ~ 5 parts of hydroxyethyl acrylate, 4 ~ 9 parts of butyl acrylate, 5 ~ 10 parts of methyl methacrylate and 50 ~ 70 parts of water.
The preparation method comprises the following steps:
(1) adding 2,2,3,4,4, 4-hexafluorobutanol into an emulsion amine-free raw material according to a mass ratio of 5 ~ 10: 1 ~ 3, introducing nitrogen for protection, stirring and mixing, distilling under reduced pressure to obtain a reduced pressure distillate a, adding a cyanate additive into the reduced pressure distillate a according to a mass ratio of 5 ~ 10: 3 ~ 7, introducing nitrogen for protection, stirring and mixing to obtain a matrix, adding acetone into the matrix according to a mass ratio of 10 ~ 20: 3 ~ 5, stirring and mixing, and distilling under reduced pressure to obtain a reduced pressure distillate b;
(2) adding a waterproof auxiliary agent and a mixed monomer into the vacuum distillate b according to the mass ratio of 5 ~ 10: 1 ~ 3: 2 ~ 5, mixing to obtain an emulsion matrix, introducing nitrogen for protection, adding potassium persulfate and trimethylolpropane into the emulsion matrix according to the mass ratio of 2 ~ 5: 1 ~ 3: 80 ~ 100, stirring and mixing, cooling to room temperature to obtain a cooling material, adding an emulsifying additive into the cooling material according to the mass ratio of 70 ~ 100: 2 ~ 5, and mixing to obtain the waterproof emulsion.
The cyanate ester additive in the step (1) is prepared by adding isophorone diisocyanate into toluene diisocyanate according to the mass ratio of 1 ~ 3: 2 ~ 5 and mixing.
The emulsifying additive is prepared by mixing 3 ~ 5 parts of OP-10, 1 ~ 4 parts of isooctyl polyoxyethylene ether, 1 ~ 3 parts of peregal O-15 and 30 ~ 60 parts of deionized water in parts by weight.
Compared with other methods, the method has the beneficial technical effects that:
(1) the amine-free raw material of the emulsion prepared by the invention is obtained by taking an amine-free functional monomer, an alcohol reaction additive and adipic acid as raw materials to carry out esterification reaction, a monomer substance containing sulfonic acid groups is introduced, the acid value of the formed emulsion is adjusted to enhance the emulsification effect of the emulsion, and the sulfonic acid groups are introduced to neutralize the emulsion when the emulsion is alkaline, so that the possibility of generating ammonia gas by hydrolysis is reduced;
(2) the waterproof auxiliary agent is prepared by taking isomeric fatty tridecanol polyoxyethylene ether and acryloyl chloride as raw materials and performing acyl chlorination reaction, introduces larger branched hydrophobic end steric hindrance, associates with a hydrophilic chain segment, can be well dissolved in an emulsion micelle and can form an effective hydrophobic association micro-area under lower functionality, and the provided association point enables a hydrophobic group not to be easily extracted and well stored in a network structure of an emulsion adhesive film, so that the hydrophobic property of the adhesive film is improved;
(3) the invention introduces the mixed monomer to improve the performance of the emulsion, improves the water repellency of the emulsion through the fluorine-containing monomer, improves the stability of the adhesive film, introduces methyl methacrylate to improve the adhesiveness of the adhesive film, and improves the wear resistance and hardness of the adhesive film through hydroxyethyl acrylate.
Detailed Description
The amine-free functional monomer is: taking any one of 1, 3-dicarboxylic acid-5-sodium sulfonate, isophthalic acid dimethyl ester-5-sodium sulfonate, isophthalic acid-5-sodium sulfonate and isophthalic acid dihydroxy ethyl ester-5-sodium sulfonate to obtain the compound.
The alcohol reaction additive is: and taking any one of 1, 4-cyclohexanedimethanol, 2, 4-trimethyl-1, 3-pentanediol, 2-dimethyl-3-neopentyl glycol hydroxypropionate and neopentyl glycol to obtain the compound.
The preparation method of the amine-free raw material of the emulsion comprises the steps of taking an amine-free functional monomer, adding an alcohol reaction additive according to the mass ratio of 2 ~ 5: 3 ~ 7, mixing, introducing nitrogen for protection, heating to 210 ~ 0220 ℃, adding pentaerythrityl diisodecyl diphosphite accounting for 0.2 ~ 10.5.5% of the mass of the amine-free functional body, stirring and mixing for 20 ~ 240min to obtain a stirring mixture, adding adipic acid into the stirring mixture at 70 ~ 80 ℃ according to the mass ratio of 40 ~ 50: 5 ~ 9, adding dibutyltin diacetate accounting for 1 ~ 5% of the mass of the stirring mixture, heating to 140 ~ 170 ℃, keeping the temperature for 1 ~ 3h, heating to 200 ~ 220 ℃, keeping the temperature for 3 ~ 8h, and carrying out reduced pressure distillation to obtain the amine-free raw material of the emulsion.
The acyl chloride additive is prepared by adding acryloyl chloride into lauroyl chloride according to the mass ratio of 4 ~ 7: 1 ~ 3 and mixing.
The preparation method of the waterproof auxiliary agent comprises the steps of taking isomeric fatty tridecanol polyoxyethylene ether, adding triethylamine to the isomeric fatty tridecanol polyoxyethylene ether according to the mass ratio of 1 ~ 3: 2 ~ 4, mixing to obtain a mixture, adding dichloromethane to the mixture according to the mass ratio of 2 ~ 05: 10 ~ 120, stirring and mixing for 30 ~ 40min at the temperature of minus 4 ~ 21 and 21 ℃ to obtain a stirring mixture a, adding dichloromethane to the mixture according to the mass ratio of 1 ~ 3: 5 ~ 10, mixing to obtain a mixed solution, dropwise adding the mixed solution into the stirring mixture a according to the mass ratio of 1 ~ 3: 5 ~ 10, controlling the dropwise adding time to be 60 ~ 90min, stirring and mixing for 10 ~ 12h at the temperature of 0 ~ 5 ℃, carrying out suction filtration, taking suction filtration residues for rotary evaporation, and carrying out vacuum drying on the rotary evaporation residues to obtain the waterproof auxiliary agent.
The cyanate additive is prepared by adding isophorone diisocyanate into toluene diisocyanate according to the mass ratio of 1 ~ 3: 2 ~ 5 and mixing.
The mixed monomer is prepared by mixing 3 ~ 7 parts of dodecafluoroheptyl methacrylate, 3 ~ 6 parts of vinyl acetate, 2 ~ 6 parts of perfluorohexyl ethyl acrylate, 2 ~ 5 parts of hydroxyethyl acrylate, 4 ~ 9 parts of butyl acrylate, 5 ~ 10 parts of methyl methacrylate and 50 ~ 70 parts of water in parts by weight.
The emulsifying additive is prepared by mixing 3 ~ 5 parts of OP-10, 1 ~ 4 parts of isooctyl polyoxyethylene ether, 1 ~ 3 parts of peregal O-15 and 30 ~ 60 parts of deionized water in parts by weight.
A method for preparing a water-repellent emulsion, comprising the steps of:
(1) adding 2,2,3,4,4, 4-hexafluorobutanol into an emulsion amine-free raw material according to a mass ratio of 5 ~ 10: 1 ~ 3, introducing nitrogen for protection, stirring and mixing at 110 ~ 0120 ℃ for 30 ~ 50min, carrying out reduced pressure distillation to obtain a reduced pressure distillate a, adding a cyanate additive into the reduced pressure distillate a according to a mass ratio of 5 ~ 10: 3 ~ 7, introducing nitrogen for protection, stirring and mixing at 70 ~ 80 ℃ for 30 ~ 50min to obtain a matrix, adding acetone into the matrix according to a mass ratio of 10 ~ 20: 3 ~ 5, stirring and mixing for 20 ~ 40min, and carrying out reduced pressure distillation to obtain a reduced pressure distillate b;
(2) adding a waterproof auxiliary agent and a mixed monomer into the vacuum distillate b according to the mass ratio of 5 ~ 10: 1 ~ 3: 2 ~ 5, mixing to obtain an emulsion matrix, introducing nitrogen for protection, adding potassium persulfate and trimethylolpropane into the emulsion matrix according to the mass ratio of 2 ~ 5: 1 ~ 3: 80 ~ 100, stirring and mixing at 70 ~ 80 ℃ for 2 ~ 5h, cooling to room temperature to obtain a cooling object, adding an emulsifying additive into the cooling object according to the mass ratio of 70 ~ 100: 2 ~ 5, and mixing to obtain the waterproof emulsion.
The amine-free functional monomer is: 1, 3-dicarboxylic acid-5-sodium sulfonate is taken.
The alcohol reaction additive is: 1, 4-cyclohexanedimethanol was taken.
The preparation method of the amine-free raw material of the emulsion comprises the following steps: taking non-amine functional monomers according to the mass ratio of 2: 3 adding an alcohol reaction additive, mixing, introducing nitrogen for protection, heating to 210 ℃, adding pentaerythritol diphosphite diisodecyl ester with the mass of 0.2% of that of the amine-free functional body, stirring and mixing for 20min to obtain a stirring mixture, and taking the stirring mixture at 70 ℃ according to the mass ratio of 40: 5 adding adipic acid, adding dibutyltin diacetate with the mass of 1% of the stirring mixture, heating to 140 ℃, preserving heat for 1h, heating to 200 ℃, preserving heat for 3h, and distilling under reduced pressure to obtain the amine-free raw material of the emulsion.
The acyl chloride additive is: taking acryloyl chloride according to the mass ratio of 4: 1 adding lauroyl chloride and mixing to obtain the final product.
The preparation method of the waterproof auxiliary agent comprises the following steps: taking isomeric fatty tridecanol polyoxyethylene ether according to the mass ratio of 1: 2, adding triethylamine, mixing to obtain a mixture, and taking the mixture according to a mass ratio of 2: 10, adding dichloromethane, stirring and mixing at-4 ℃ for 30min to obtain a stirring mixture a, taking acyl chloride additive according to the mass ratio of 1: and 5, adding dichloromethane, mixing to obtain a mixed solution, and taking the mixed solution according to a mass ratio of 1: and 5, dropwise adding the mixture into the stirred mixture a, controlling the dropwise adding time to be 60min, stirring and mixing at 0 ℃ for 10h, carrying out suction filtration, taking suction filtration residues for rotary evaporation, taking rotary evaporation residues, and carrying out vacuum drying to obtain the waterproof auxiliary agent.
The cyanate ester additive is: taking isophorone diisocyanate according to a mass ratio of 1: 2 adding toluene diisocyanate and mixing to obtain the product.
The mixed monomers are as follows: according to the mass parts, 3 parts of dodecafluoroheptyl methacrylate, 3 parts of vinyl acetate, 2 parts of perfluorohexyl ethyl acrylate, 2 parts of hydroxyethyl acrylate, 4 parts of butyl acrylate, 5 parts of methyl methacrylate and 50 parts of water are mixed to obtain the water-soluble acrylic acid.
The emulsifying additive is as follows: according to the mass portion, 3 portions of OP-10, 1 portion of isooctyl polyoxyethylene ether, 1 portion of peregal O-15 and 30 portions of deionized water are mixed to obtain the product.
A method for preparing a water-repellent emulsion, comprising the steps of:
(1) mixing emulsion amine-free raw materials according to a mass ratio of 5: 1, adding 2,2,3,4,4, 4-hexafluorobutanol, introducing nitrogen for protection, stirring and mixing at 110 ℃ for 30min, carrying out reduced pressure distillation to obtain a reduced pressure distillate a, and taking the reduced pressure distillate a according to a mass ratio of 5: 3 adding a cyanate ester additive, introducing nitrogen for protection, stirring and mixing at 70 ℃ for 30min to obtain a matrix, and mixing the matrix according to a mass ratio of 10: 3 adding acetone, stirring and mixing for 20min, and distilling under reduced pressure to obtain a reduced pressure distillate b;
(2) taking the reduced pressure distillate b according to a mass ratio of 5: 1: 2, adding a waterproof auxiliary agent and a mixed monomer, mixing to obtain an emulsion matrix, introducing nitrogen for protection, and taking potassium persulfate and trimethylolpropane according to a mass ratio of 2: 1: 80, adding the mixture into the emulsion matrix, stirring and mixing the mixture for 2 hours at the temperature of 70 ℃, cooling the mixture to room temperature to obtain a cooled substance, and taking the cooled substance according to a mass ratio of 70: 2 adding an emulsifying additive and mixing to obtain the waterproof emulsion.
The amine-free functional monomer is: dimethyl isophthalate-5-sodium sulfonate is taken.
The alcohol reaction additive is: taking 2,2, 4-trimethyl-1, 3-pentanediol.
The preparation method of the amine-free raw material of the emulsion comprises the following steps: taking non-amine functional monomers according to a mass ratio of 5: 7 adding an alcohol reaction additive, mixing, introducing nitrogen for protection, heating to 220 ℃, adding pentaerythritol diphosphite diisodecyl ester with the mass of 0.5% of that of the amine-free functional body, stirring and mixing for 40min to obtain a stirring mixture, and taking the stirring mixture at 80 ℃ according to the mass ratio of 50: 9 adding adipic acid, adding dibutyltin diacetate with the mass of 5% of the stirring mixture, heating to 170 ℃, preserving heat for 3 hours, heating to 220 ℃, preserving heat for 8 hours, and distilling under reduced pressure to obtain the amine-free raw material of the emulsion.
The acyl chloride additive is: taking acryloyl chloride according to the mass ratio of 7: 3 adding lauroyl chloride and mixing to obtain the final product.
The preparation method of the waterproof auxiliary agent comprises the following steps: taking isomeric fatty tridecanol polyoxyethylene ether according to the mass ratio of 3: 4, adding triethylamine, mixing to obtain a mixture, and taking the mixture according to a mass ratio of 5: adding dichloromethane into the mixture 20, stirring and mixing the mixture at the temperature of 1 ℃ for 40min to obtain a stirred mixture a, and mixing the acyl chloride additive according to the mass ratio of 3: 10, adding dichloromethane, mixing to obtain a mixed solution, and taking the mixed solution according to a mass ratio of 3: and (3) dropwise adding 10 into the stirred mixture a, controlling the dropwise adding time to be 90min, stirring and mixing at 5 ℃ for 12h, carrying out suction filtration, taking suction filtration residues for rotary evaporation, taking rotary evaporation residues, and carrying out vacuum drying to obtain the waterproof auxiliary agent.
The cyanate ester additive is: taking isophorone diisocyanate according to a mass ratio of 3: and 5, adding toluene diisocyanate and mixing to obtain the product.
The mixed monomers are as follows: according to the mass parts, 7 parts of dodecafluoroheptyl methacrylate, 6 parts of vinyl acetate, 6 parts of perfluorohexyl ethyl acrylate, 5 parts of hydroxyethyl acrylate, 9 parts of butyl acrylate, 10 parts of methyl methacrylate and 70 parts of water are mixed to obtain the water-soluble acrylic acid.
The emulsifying additive is as follows: according to the mass parts, 5 parts of OP-10, 4 parts of isooctyl polyoxyethylene ether, 3 parts of peregal O-15 and 60 parts of deionized water are mixed to obtain the catalyst.
A method for preparing a water-repellent emulsion, comprising the steps of:
(1) mixing emulsion amine-free raw materials according to a mass ratio of 10: 3, adding 2,2,3,4,4, 4-hexafluorobutanol, introducing nitrogen for protection, stirring and mixing at 120 ℃ for 50min, carrying out reduced pressure distillation to obtain a reduced pressure distillate a, and taking the reduced pressure distillate a according to a mass ratio of 10: 7 adding a cyanate ester additive, introducing nitrogen for protection, stirring and mixing at 80 ℃ for 50min to obtain a matrix, and mixing the matrix according to a mass ratio of 20: 5 adding acetone, stirring and mixing for 40min, and distilling under reduced pressure to obtain a reduced pressure distillate b;
(2) taking the reduced pressure distillate b according to the mass ratio of 10: 3: 5, adding a waterproof auxiliary agent and a mixed monomer, mixing to obtain an emulsion matrix, introducing nitrogen for protection, and taking potassium persulfate and trimethylolpropane according to a mass ratio of 5: 3: 100, adding the mixture into an emulsion matrix, stirring and mixing the mixture for 5 hours at the temperature of 80 ℃, cooling the mixture to room temperature to obtain a cooled substance, and taking the cooled substance according to the mass ratio of 100: 5 adding an emulsifying additive and mixing to obtain the waterproof emulsion.
The amine-free functional monomer is: taking m-phthalic acid-5-sodium sulfonate.
The alcohol reaction additive is: taking 2, 2-dimethyl-3-hydroxyl neopentyl glycol propionate.
The preparation method of the amine-free raw material of the emulsion comprises the following steps: taking non-amine functional monomers according to the mass ratio of 3: 4 adding an alcohol reaction additive, mixing, introducing nitrogen for protection, heating to 215 ℃, adding pentaerythritol diphosphite diisodecyl ester with the mass of 0.3% of that of the amine-free functional body, stirring and mixing for 30min to obtain a stirring mixture, and taking the stirring mixture at 75 ℃ according to the mass ratio of 45: 6, adding adipic acid, adding dibutyltin diacetate with the mass of 4% of the stirring mixture, heating to 150 ℃, preserving heat for 2 hours, heating to 210 ℃, preserving heat for 5 hours, and distilling under reduced pressure to obtain the amine-free raw material of the emulsion.
The acyl chloride additive is: taking acryloyl chloride according to the mass ratio of 5: 2 adding lauroyl chloride and mixing to obtain the final product.
The preparation method of the waterproof auxiliary agent comprises the following steps: taking isomeric fatty tridecanol polyoxyethylene ether according to the mass ratio of 2: and 3, adding triethylamine, mixing to obtain a mixture, and taking the mixture according to a mass ratio of 4: 15, adding dichloromethane, stirring and mixing at-2 ℃ for 35min to obtain a stirring mixture a, taking acyl chloride additive according to the mass ratio of 2: 7, adding dichloromethane, mixing to obtain a mixed solution, and taking the mixed solution according to a mass ratio of 2: 7, dropwise adding into the stirred mixture a, controlling the dropwise adding time for 80min, stirring and mixing at 4 ℃ for 11h, carrying out suction filtration, taking suction filtration residues for rotary evaporation, taking rotary evaporation residues, and carrying out vacuum drying to obtain the waterproof auxiliary agent.
The cyanate ester additive is: taking isophorone diisocyanate according to a mass ratio of 2: 3 adding toluene diisocyanate and mixing to obtain the product.
The mixed monomers are as follows: according to the mass parts, 5 parts of dodecafluoroheptyl methacrylate, 4 parts of vinyl acetate, 3 parts of perfluorohexyl ethyl acrylate, 4 parts of hydroxyethyl acrylate, 5 parts of butyl acrylate, 7 parts of methyl methacrylate and 60 parts of water are mixed to obtain the water-soluble acrylic acid.
The emulsifying additive is as follows: and mixing 4 parts of OP-10, 2 parts of isooctyl polyoxyethylene ether, 2 parts of peregal O-15 and 50 parts of deionized water according to the mass parts to obtain the catalyst.
A method for preparing a water-repellent emulsion, comprising the steps of:
(1) mixing emulsion amine-free raw materials according to a mass ratio of 7: 2, adding 2,2,3,4,4, 4-hexafluorobutanol, introducing nitrogen for protection, stirring and mixing at 115 ℃ for 40min, carrying out reduced pressure distillation to obtain a reduced pressure distillate a, and taking the reduced pressure distillate a according to a mass ratio of 7: 4 adding a cyanate ester additive, introducing nitrogen for protection, stirring and mixing at 75 ℃ for 40min to obtain a matrix, and taking the matrix according to a mass ratio of 15: 4 adding acetone, stirring and mixing for 30min, and distilling under reduced pressure to obtain a reduced pressure distillate b;
(2) taking the reduced pressure distillate b according to the mass ratio of 7: 2: 3, adding a waterproof auxiliary agent and a mixed monomer, mixing to obtain an emulsion matrix, introducing nitrogen for protection, and taking potassium persulfate and trimethylolpropane according to a mass ratio of 3: 2: 90, adding the mixture into the emulsion matrix, stirring and mixing the mixture for 3 hours at the temperature of 75 ℃, cooling the mixture to room temperature to obtain a cooled substance, and taking the cooled substance according to the mass ratio of 90: 3 adding an emulsifying additive and mixing to obtain the waterproof emulsion.
Comparative example 1: essentially the same procedure as in example 2 was followed except that the amine-free starting material of the emulsion was absent.
Comparative example 2: the procedure was essentially the same as that used in example 2, except that the water-proofing aid was absent.
Comparative example 3: essentially the same procedure as in example 2, except that the mixed monomers were absent.
Comparative example 4: waterproof emulsion produced by a company of Nantong City.
The waterproof emulsions prepared in the above examples and comparative examples were tested to determine the tensile strength and elongation at break of the waterproof emulsion coating film according to the GB/T23445-2009 standard; the permeation resistance pressure was measured according to the test method of JC/T2217-2014, the ammonia release from the water-repellent paint was measured, and the results obtained by the titration method after distillation are shown in Table 1.
Table 1:
| detecting items | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Tensile strength/MPa | 2.7 | 2.9 | 2.8 | 2.3 | 2.2 | 2.4 | 1.9 |
| Elongation at break/% | 96 | 110 | 98 | 84 | 83 | 81 | 70 |
| Osmotic pressure resistance/MPa | 1.6 | 1.8 | 1.7 | 1.2 | 1.3 | 1.0 | 0.6 |
| X Ammonia/g/kg | 0 | 0 | 0 | 0.1 | 0.3 | 0.1 | 1.6 |
In summary, it can be seen from table 1 that the waterproof emulsion of the present invention is more effective and is worth popularizing, and the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The waterproof emulsion is characterized by comprising an amine-free raw material, a waterproof auxiliary agent and a mixed monomer.
2. The waterproof emulsion according to claim 1, wherein the amine-free raw material of the emulsion is prepared by adding an alcohol reaction additive into an amine-free functional monomer according to a mass ratio of 2 ~ 5: 3 ~ 7, mixing, introducing nitrogen for protection, adding pentaerythritol diisodecyl diphosphite accounting for 0.2 ~ 0.5.5% of the mass of the amine-free functional body, stirring and mixing to obtain a stirred mixture, adding adipic acid into the stirred mixture according to a mass ratio of 40 ~ 50: 5 ~ 9, adding dibutyltin diacetate accounting for 1 ~ 5% of the mass of the stirred mixture, heating to 140 ~ 170 ℃, keeping the temperature, heating to 200 ~ 220 ℃, keeping the temperature, and distilling under reduced pressure to obtain the amine-free raw material of the emulsion.
3. The water-repellent emulsion according to claim 2, characterized in that said non-amine functional monomer is: taking any one of 1, 3-dicarboxylic acid-5-sodium sulfonate, isophthalic acid dimethyl ester-5-sodium sulfonate, isophthalic acid-5-sodium sulfonate and isophthalic acid dihydroxy ethyl ester-5-sodium sulfonate to obtain the compound.
4. The water-repellent emulsion according to claim 2, wherein the alcohol-reactive additive is: and taking any one of 1, 4-cyclohexanedimethanol, 2, 4-trimethyl-1, 3-pentanediol, 2-dimethyl-3-neopentyl glycol hydroxypropionate and neopentyl glycol to obtain the compound.
5. The waterproof emulsion according to claim 1, wherein the waterproof auxiliary agent is prepared by adding triethylamine to isomeric fatty tridecanol polyoxyethylene ether in a mass ratio of 1 ~ 3: 2 ~ 4 to obtain a mixture, adding dichloromethane to the mixture in a mass ratio of 2 ~ 5: 10 ~ 20 to obtain a stirred mixture a, adding dichloromethane to the mixture in a mass ratio of 1 ~ 3: 5 ~ 10 to obtain a mixed solution, adding the mixed solution dropwise to the stirred mixture a in a mass ratio of 1 ~ 3: 5 ~ 10 to obtain a mixed solution, controlling the dropwise adding time to 60 ~ 90min, stirring and mixing, carrying out suction filtration, taking the residue to carry out rotary evaporation, and carrying out vacuum drying on the residue to obtain the waterproof auxiliary agent.
6. The waterproof emulsion according to claim 5, wherein the acid chloride additive is prepared by mixing lauroyl chloride with acryloyl chloride at a mass ratio of 4 ~ 7: 1 ~ 3.
7. The water-repellent emulsion according to claim 1, wherein the mixed monomer is obtained by mixing, in parts by mass, 3 ~ 7 parts of dodecafluoroheptyl methacrylate, 3 ~ 6 parts of vinyl acetate, 2 ~ 6 parts of perfluorohexylethyl acrylate, 2 ~ 5 parts of hydroxyethyl acrylate, 4 ~ 9 parts of butyl acrylate, 5 ~ 10 parts of methyl methacrylate, and 50 ~ 70 parts of water.
8. A process for preparing a water-repellent emulsion according to any one of claims 1 ~ 7, comprising the steps of:
(1) adding 2,2,3,4,4, 4-hexafluorobutanol into an emulsion amine-free raw material according to a mass ratio of 5 ~ 10: 1 ~ 3, introducing nitrogen for protection, stirring and mixing, distilling under reduced pressure to obtain a reduced pressure distillate a, adding a cyanate additive into the reduced pressure distillate a according to a mass ratio of 5 ~ 10: 3 ~ 7, introducing nitrogen for protection, stirring and mixing to obtain a matrix, adding acetone into the matrix according to a mass ratio of 10 ~ 20: 3 ~ 5, stirring and mixing, and distilling under reduced pressure to obtain a reduced pressure distillate b;
(2) adding a waterproof auxiliary agent and a mixed monomer into the vacuum distillate b according to the mass ratio of 5 ~ 10: 1 ~ 3: 2 ~ 5, mixing to obtain an emulsion matrix, introducing nitrogen for protection, adding potassium persulfate and trimethylolpropane into the emulsion matrix according to the mass ratio of 2 ~ 5: 1 ~ 3: 80 ~ 100, stirring and mixing, cooling to room temperature to obtain a cooling material, adding an emulsifying additive into the cooling material according to the mass ratio of 70 ~ 100: 2 ~ 5, and mixing to obtain the waterproof emulsion.
9. The method for preparing the water-proof emulsion according to claim 8, wherein the cyanate ester additive in the step (1) is prepared by adding isophorone diisocyanate into toluene diisocyanate according to a mass ratio of 1 ~ 3: 2 ~ 5 and mixing.
10. The preparation method of the waterproof emulsion as claimed in claim 8, wherein the emulsifying additive is prepared by mixing 3 ~ 5 parts of OP-10, 1 ~ 4 parts of isooctyl polyoxyethylene ether, 1 ~ 3 parts of peregal O-15 and 30 ~ 60 parts of deionized water in parts by weight.
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